O-[methyl (7,8,9-tri-O-acetyl-4,5-O,N-carbonyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosyl)onate]-(2->6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose | 929882-36-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: O-[methyl (7,8,9-tri-O-acetyl-4,5-O,N-carbonyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosyl)onate]-(2->6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose
• 英文别名: O-(methyl 5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-D-glycero-α-D-galactonon-2-ulopyranosylonate)-(2→6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose；methyl (7,8,9-tri-O-acetyl-5,4-N,O-carbonyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranoside)onate-(2->6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranoside；methyl (3aR,4R,6R,7aS)-2-oxo-6-[[(1S,2R,6R,8R,9S)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-8-yl]methoxy]-4-[(1S,2R)-1,2,3-triacetyloxypropyl]-3a,4,7,7a-tetrahydro-3H-pyrano[3,4-d][1,3]oxazole-6-carboxylate
• CAS: 929882-36-0
• 化学式: C₂₉H₄₁NO₁₇
• 分子量: 675.641
• InChiKey: AEHOTLNEHNCNGC-WKEIHNGESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  47
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  208
• 氢给体数：
  1
• 氢受体数：
  17

反应信息

• 作为反应物：
  描述：

  O-[methyl (7,8,9-tri-O-acetyl-4,5-O,N-carbonyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosyl)onate]-(2->6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose 在 barium dihydroxide 作用下， 以 乙醇 为溶剂， 反应 16.0h， 以95%的产率得到(2R,4S,5R,6R)-5-amino-4-hydroxy-2-[[(1S,2R,6R,8R,9S)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-8-yl]methoxy]-6-[(1R,2R)-1,2,3-trihydroxypropyl]oxane-2-carboxylic acid
  参考文献：
  名称：

  Application of 4,5-O,N-oxazolidinone protected thiophenyl sialosyl donor to the synthesis of α-sialosides

  摘要：

  The synthesis of a novel oxazolidinone sialosyl donor is reported. The introduction of a trans-fused ring enhances reactivity and stereoselectivity in glycosylation reactions for the synthesis of alpha-sialosides. The oxazolidinone ring can also be removed under basic conditions to afford the deprotected amine, which can be further functionalized. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.12.061
• 作为产物：
  描述：

  methyl S-4-methylphenyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2-thio-D-glycero-α-D-galacto-2-nonulopyranosidonate 在 吡啶 、 N-碘代丁二酰亚胺 、 甲烷磺酸 、 乙酸酐 、 碳酸氢钠 作用下， 以 甲醇 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 1.5h， 生成 O-[methyl (7,8,9-tri-O-acetyl-4,5-O,N-carbonyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosyl)onate]-(2->6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose
  参考文献：
  名称：

  Comparative studies on the O-sialylation with four different α/β-oriented (N-acetyl)-5-N,4-O-carbonyl-protected p-toluenethiosialosides as donors

  摘要：

  Four types of 5-N,4-O-carbonyl-protected p-toluenethiosialosides were synthesized and their couplings with different acceptors were thoroughly investigated. The results indicate that the sialyl donor structure, the amount of glycosyl acceptor, and the detailed promotion conditions have great influence on the sialylation stereoselectivties and product yields. Under the (p-Tol)(2)SO/Tf2O activation conditions, the glycosylations with simple alcohols provided declined alpha-selectivities and higher yields with increasing the amounts of acceptors from 1.1 equiv to 2.0 equiv. However, the outcome of same sialylation was independent of the relative amounts of sugar alcohol acceptors. With NIS/TfOH as promoter, the alpha-selectivities of the sialylations were significantly improved compared with the cases activated by (p-Tol)(2)SO/Tf2O. In general, the difference in configuration of N-acetylated sialyl donors (D2 and D4) has little effect on the sialylation yield and stereoselectivity. In contrast, the N-deacetylated alpha/beta sialyl donors (D1 and D3) show complex sialylation profiles with different acceptors. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2014.02.006

文献信息

• Solvent Effect in the Synthesis of Sialosyl α(2-6) Galactosides: Is Acetonitrile the only Choice?
  作者：Cristina De Meo、Michael Farris、Nathan Ginder、Bonnie Gulley、Uvege Priyadarshani、Matthew Woods

  DOI：10.1002/ejoc.200800278

  日期：2008.7

  In spite of notable achievements for the synthesis of α-sialosides that have been made in the past decades, sialylation reactions often require low temperatures (–40 to –78 °C) and the use of acetonitrile as a solvent. Herein we report that a C-5 oxazolidinone sialosyl donor gives high yields andstereoselectivities in the presence of dichloromethane and/or tetrahydrofuran at 0 °C. Surprisingly, high

  尽管过去几十年在合成 α-唾液酸苷方面取得了显著成就，但唾液酸化反应通常需要低温（–40 至 –78 °C）并使用乙腈作为溶剂。在本文中，我们报告了 C-5 恶唑烷酮唾液酸供体在二氯甲烷和/或四氢呋喃存在下在 0°C 下具有高产率和立体选择性。令人惊讶的是，即使在环境温度下，在四氢呋喃中也能获得高立体选择性和产率。（© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008）
• C-5 Modified S-Benzoxazolyl Sialyl Donors: Towards More Efficient Selective Sialylations
  作者：Benjamin N. Harris、Payal P. Patel、Chase P. Gobble、Matthew J. Stark、Cristina De Meo

  DOI：10.1002/ejoc.201100539

  日期：2011.7

  We previously reported that the selective activation of an S-benzoxazolyl (SBox) sialyl donor over a galactosyl acceptor equipped with a thioethyl anomeric moiety can be performed in high yield but with poor stereoselectivity. To optimize this strategy, which allows the synthesis of complex carbohydrates to be shortened, a range of SBox sialyl donors modified at C-5 were synthesized and tested. In

  我们之前报道过 S-苯并恶唑基 (SBox) 唾液酸供体在配备有硫乙基异头部分的半乳糖基受体上的选择性活化可以以高产率进行，但立体选择性较差。为了优化这一策略，缩短复杂碳水化合物的合成，合成并测试了一系列在 C-5 处修饰的 SBox 唾液酸供体。特别是，SBox 离去基团和 C-4,5 的恶唑烷酮的组合​​允许在各种溶剂和不同温度下实现出色的立体控制。在二氯甲烷/四氢呋喃 (1:1) 溶剂系统中，在三氟甲磺酸铋 (III) 存在下获得了几乎完全的立体选择性。
• Donor‐Reactivity‐Controlled Sialylation Reactions
  作者：Kesatebrhan Haile Asressu、Chun‐Wei Chang、Sarah Lam、Cheng‐Chung Wang

  DOI：10.1002/ejoc.202100718

  日期：2021.8.26

  AbstractAlthough tremendous efforts have been made for the efficient preparation of sialosides, controlling the stereochemical outcome of sialylation reaction still remains one of the most challenging tasks due to the unique chemical structure of sialic acid. We developed a new strategy to statistically analyze the stereoselectivity of sialylation reactions on six types of p‐tolyl thiosialosides in NIS/TfOH system using Relative Reactivity Value (RRV) as the indicator. Analysis of the reaction mechanism showed the formation of the relatively stable glycosyl bromide and glycosyl chloride intermediates from halide‐ and triflate‐containing promotors in the absence of an acceptor. We found that the α/β‐stereoselectivity, yields, and intermediate changes were associated with their donor reactivity. These findings enable to tailor the most suitable building blocks for stereo‐controlled sialylation reactions.
• Studies on the sialylation of galactoses with different C-5 modified sialyl donors
  作者：Jianzhi Gong、Han Liu、John M. Nicholls、Xuechen Li

  DOI：10.1016/j.carres.2012.08.007

  日期：2012.11

  Synthetic sialylated glycans provide useful tools to study carbohydrate-mediated biological recognition; however chemical sialylation is the most challenging practice in preparative carbohydrate chemistry, which is often associated with low yields and poor stereoselectivity. Herein, we conducted extensive studies on sialylation with five types of 5-N-modified sialyl donors and four types of galactosyl acceptors. Our studies have shown that a good combination between the donor and the acceptor seems necessary to achieve high yield and stereoselectivity. None of the donors or acceptors showed 'universal' utility toward the sialylation reaction. (C) 2012 Elsevier Ltd. All rights reserved.